Gasoline compositions



United States Patent O-fiice 3, ,2 1 Patented Mar. 24, 1964 3,126,261GASOLINE COMPOSITIONS Patrick J. Friel, Broomall, Pa., assignor to SunOil Company, Philadelphia, Pa., a corporation of New Jersey No Drawing.Filed Mar. 28, 1958, Ser. No. 724,517 4 Claims. (Cl. 44-69) Thisinvention relates to novel gasoline compositions containing additiveswhich suppress surface ignition and spark plug fouling in spark ignitioninternal combustion engines.

Surface ignition is the ignition, prior to normal ignition by the sparkplug, of engine fuel by glowing or burning carbonaceous material whichis deposited on engine combustion chamber surfaces. These carbonaceousdeposits are derived from decomposition of the fuel and/ or lubricantused in the engine. Also contained in engine deposits are productsresulting from decomposition of fuel or lubricant additives. Thepresence in engine deposits of decomposition products of organometallicanti-knock additives such as tetraethyl lead is especially deleterioussince these products catalyze ignition of carbonaceous fuel and/ orlubricant decomposition products at low temperatures thereby greatlyincreasing surface ignition in an engine. Surface igintion isdeleterious in that it causes loss of power, increased engine wear andincreased engine fuel octane requirement necessary for knock-freeperformance. The octane requirement increase (O.R.I.) of an engine whileoperating on a particular fuel is indicative of the surface ignitionpromoting tendencies of that fuel.

Spark plug fouling is caused by the deposition on spark plugs of leadanti-knock additive decomposition products either which themselvesconduct electricity, or which are reduced under combustion chamberconditions to products which conduct electricity. A build-up on thespark plugs of such products provides an alternate path for spark plugcurrent and results in fouling or shorting out of the spark plugs.

Now, in accordance with the present invention, a dialkylborino-phosphine or mixture of such compounds is added in minor amountto gasoline containing organo-lead anti-knock additives to suppresssurface ignition and spark plug fouling.

In an embodiment of the invention, one or more dialkyl borino phosphineis incorporated in a gasoline containing an organo-lead anti-knock agentwhereby spark plug fouling, O.R.I., and surface iginition aresubstantially suppressed.

Included in the novel gasoline compositions of the invention is a smallamount, SlllfiClGll't to suppress engine O.R.I. surface ignition andspark plug fouling, of a dialkyl borino phosphine or a mixture of suchcompounds. Dialkyl borino phosphines have the general formula:

Rn wherein R and R are alkyl radicals, i.e., saturated aliphatichydrocarbon radicals. In accordance with the practice of this invention,the alkyl radicals, R and R can be the same or different, but eachradical preferably contains not more than 6 carbon atoms in eitherstraight or branched chain configuration. These alkyl radicals can alsocontain halogen substituents. Examples of dialkyl borino phosphineswhich can be employed as additives include dimethyl borino phosphine,diethyl borino phosphine, di-n-propyl borino phosphine, di-i-propylborino phosphine, di-n-butyl borino phosphine, di-n-pentyl borinophosphine, di-n-hexyl borino phosphine, methylethyl borino phosphine,methyl-n-propyl borino phosphine, ethyl-n-butyl borino phosphine and thelike. The

use of di-n-butyl borino phosphine is particularly preferred in thepractice of this invention.

The dialkyl borino phosphines can be prepared by reacting a trialkylborine with phosphorus trichloride to produce the corersponding dialkylborino chloride, generally a high boiling liquid. A solution of thelatter product in solvents such as a mixture of benzene andtriethylamine, when reacted with gaseous phosphine, yields thecorresponding dialkyl borino phosphine. The latter compounds aregenerally high boiling liquids which are sufliciently soluble ingasoline hydrocarbons, within the range of concentrations contemplatedby the instant inven tion, so as not to require the use of mutualsolvents or dispersants. Where necessary, however, such mutual sol ventsand dispersants can be employed in order to incorporate amounts of theadditive in excess of its solubility in the leaded gasoline composition.

The novel gasoline compositions of the invention comprise mainlypetroleum hydrocarbons boiling in the gasoline range of from about F. toabout 440 F. at atmospheric pressure, and usually from about F. to about400 F. Both automotive gasoline and aviation gasoline are within thescope of this invention. Aviation.

gasoline has a more closely specified atmospheric boiling range,generally extending from a minimum of about F. to a maximum of about 350F.

The gasoline compositions of the invention also contain an anti-knockamount of an organo-lead anti-knock agent. Tetraethyl lead (TEL) is themost commonly used organo-lead anti-knock compound although otherorgano-lead compounds such as tetramethyl lead, tetraphenyl lead,tetraisopropyl lead, triethyl methyl lead, diethyl dimethyl lead andtetramethyl lead are sometimes used. Mixtures of these compounds canalso be used. In automotive gasolines the organo-lead anti-knockcompounds are used in amounts ranging from about 0.5 to 3.0 cc. of thecompound per gallon of gasoline, while in aviation gasolines a greateramount can be used, viz., up to about 6.0 cc. per gallon. Along with theorganolead anti-knock compound, various volatile halohydrocarbons arenormally incorporated in the gasoline in lead scavenging amounts, i.e.,in amounts theoretically calculated to convert the lead in theorgano-lead compound to volatile compounds, viz., lead dihalides.Examples of such halohydrocarbon lead scavengers are: organobromides and-chlorides such as ethylene dibromide, ethylene dichloride, acetylenetetrabromide, hexachloropropylene and mixtures thereof; monoandpolyhalopropanes, butanes and pentanes; polyhaloalkyl benzenes; andmixtures thereof with each other and the like. It is therefore to beclearly understood that the novel additives of this invention can beused in leaded gasoline compositions either with or without all suchlead scavengers as are commonly employed, and in such amounts as may berequired.

It is to be understood that all other gasoline additives commonlyemployed in the art such as, for example, anti-icing agents, scavengers,detergents, corrosion inhibitors, stabilizers, dyes and the like, canalso be employed in the novel gasoline compositions of the inventioncontaining an organo-lead anti-knock agent.

The novel additives of this invention, viz., the dialkyl borinophosphines, are added to the gasoline composition containing anorgano-lead anti-knock additive in a small amount suflicient to suppresssurface ignition, O.R.I., and spark plug fouling in subsequent engineoperation. The amount of additive employed will normally depend upon theamount of organo-metallic anti-knock agent also present in the fuelcomposition. Generally, amounts of the additive, or mixture ofadditives, in the range of from about 0.005% to about 1.0% by weight 3of the resulting gasoline composition, and preferably 0.01% to 0.50%give good results. On occasion, amounts outside of the above-citedranges can be used.

In order to illustrate a specific embodiment of this invention,di-n-butyl borino phosphine is produced by reacting tri-n-butyl borinewith phosphorus trichloride and subsequently reacting a solution of thedi-n-butyl borino chloride in benzene and triethylamine with phosphinegas.

The benzene and triethylamine are removed by distil lation leaving aliquid product boiling above about 250 C. and consisting of di-n-butylborino phosphine. The above-prepared additive is incorporated in acommercial high octane automotive gasoline in an amount equivalent to0.01% by weight of the resulting gasoline composition. The commercialgasoline employed also contains 3 cc. per gallon of tetraethyl lead andthe customary accompanying amount of halohydrocarbon lead scavengers.The resulting fuel composition has a Research octane number of 103.2(ASTM-D908) and illustrates the novel gasoline compositions of theinstant invention.

A standard Oldsmobile engine employing a commercially available highcompression S.A.Ev No. W30 petroleum lubricating oil is used inevaluating the above novel gasoline composition. This engine has acompression ratio of 10:1 and an initial fuel Research octane numberrequirement (for knock-free performance) of 96. When the engine isoperated according to a standard simulated high speed test procedure fora period of 95 hours on the novel gasoline composition of the invention,the final octane requirement is 98 ON, equivalent to an octanerequirement increase (O.R.I.) of only 2 numbers. However, when theengine is operated according to the same procedure and for the sameperiod of time on the identical leaded base gasoline, but without theadditives of the invention, the O.R.I. is found to be 4 numbers. Thus itcan be seen that employment of the novel gasoline compositions of thisinvention results in a substantial reduction in engine O.R.I. which, inturn, is indicative of a significant decrease in the surface ignitiontendencies of the leaded base fuel.

Other fuel compositions within the scope of this invention, whenemployed as herein described, give substantially equivalent results.

The invention claimed is:

1. Spark ignition internal combustion engine fuel composition consistingessentially of mainly petroleum hydrocarbons boiling within the gasolinerange; an anti-knock amount of an organo-lead anti-knock compound, and asmall amount, sufiicient to suppress engine surface ignition and octanerequirement increase of an additive material having the general formula:

R2 wherein R and R are alkyl radicals containing not more than 6 carbonatoms each.

2. Composition according to claim 1 wherein said organ-lead compound istetraethyl lead.

3. Composition according to claim 2 wherein said additive material isdi-n-butyl borino phosphine.

4. A gasoline containing an antiknock quantity of tetraalkyl lead and asmall amount, sufficient to suppress preignition, of an organic boronandphosphorus-containing compound having the general formula:

wherein R and R are lower molecular weight alkyl radi cals.

References Cited in the file of this patent UNITED STATES PATENTS2,257,194 Rosen Sept. 30, 1941 2,265,819 Rosen Dec. 9, 1941 2,368,866Nygaard et al Feb. 6, 1945 2,710,251 Darling June 7, 1955 2,720,448Arimoto Oct. 11, 1955 2,797,153 Bereslavsky June 25, 1957 2,818,417Brown et al. Dec. 31, 1957 2,821,463 Scott et al. Ian. 28, 1958 FOREIGNPATENTS 795,067 Great Britain May 14, 1958 OTHER REFERENCES ChemicalSociety Journal (London), February 1953, The Reaction of Diborane WithAlkyl Derivatives of Some Group V-B Elements, by Hewitt et al., pages530 to 534.

Chemical Reviews, vol. 58, No. 1, February 1958, Stability RelationshipsAmong Analogous Molecular Addition Compounds of Group III Elements, byStone, pages 101 to 129.

1. SPARK IGNITION INTERNAL COMBUSTION ENGINE FUEL COMPOSITION CONSISTINGESSENTIALLY OF MAINLY PETROLEUM HYDROCARBONS BOILING WITHIN THE GASOLINERANGE; AND ANTI-KNOCK AMOUNT OF AN ORGANO-LEAD ANTI-KNOCK COMPOUND, ANDA SMALL AMOUNT, SUFFICIENT TO SUPPRESS ENGINE SURFACE IGNITION ANDOCTANE REQUIREMENT INCREASE OF AN ADDITIVE MATERIAL HAVING THE GENERALFORMULA: R1-B(-R2)-PH2 WHEREIN R1 AND R2 ARE ALKYL RADICALS CONTAININGNOT MORE THAN 6 CARBON ATOMS EACH.